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Volumn 68, Issue 20, 2003, Pages 7582-7590

Influence of the nitroxide structure on the homolysis rate constant of alkoxyamines: A Taft-Ingold analysis

Author keywords

[No Author keywords available]

Indexed keywords

BOND CLEAVAGE;

EID: 0141655087     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo030036k     Document Type: Article
Times cited : (88)

References (90)
  • 6
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    • American Chemical Society: Washington, DC; Chapter 11, and references therein
    • (c) Fukuda, T.; Goto, A.; Ohno, K.; Tsujii, Y. ACS Symposium Series 685; American Chemical Society: Washington, DC, 1998; Chapter 11, p 180 and references therein.
    • (1998) ACS Symposium Series 685 , pp. 180
    • Fukuda, T.1    Goto, A.2    Ohno, K.3    Tsujii, Y.4
  • 29
    • 0035781101 scopus 로고    scopus 로고
    • and references therein
    • (h) Fischer, H. Chem. Rev. 2001, 101, 3581 and references therein.
    • (2001) Chem. Rev. , vol.101 , pp. 3581
    • Fischer, H.1
  • 52
    • 0003684028 scopus 로고
    • Bawden, D., Ed.; Research Studies Press, J. Wiley & Sons: New York
    • Shorter, J. In Correlation Analysis of Organic Reactivity; Bawden, D., Ed.; Research Studies Press, J. Wiley & Sons: New York, 1982.
    • (1982) Correlation Analysis of Organic Reactivity
    • Shorter, J.1
  • 68
    • 0141584960 scopus 로고    scopus 로고
    • note
    • c simply for easiness, although Hancock's correction seems to have no meanings (see refs 33, 54).
  • 69
    • 0141696660 scopus 로고    scopus 로고
    • note
    • a for an expected equivalent steric strain), the ratio a/b can be assumed close to 1. Consequently, being the simplest solution, a = b = 1 should be used with each nitroxyl moiety; any other possibility involves simply a scaling factor of δ.
  • 72
    • 0141473369 scopus 로고    scopus 로고
    • note
    • Equivalent values were found with couple (12,13) and (8,9), -0.61 and -0.83, respectively.
  • 76
    • 85050568457 scopus 로고
    • Allinger, N. L., Eliel, E. L., Eds.; Wiley-Interscience: New York
    • Janzen, E. G. In Topics in Stereochemistry; Allinger, N. L., Eliel, E. L., Eds.; Wiley-Interscience: New York, 1971; Vol. 6, pp 177-217.
    • (1971) Topics in Stereochemistry , vol.6 , pp. 177-217
    • Janzen, E.G.1
  • 77
    • 0141584958 scopus 로고    scopus 로고
    • note
    • s = -0.75.
  • 80
    • 0141808066 scopus 로고    scopus 로고
    • note
    • a for molecule 5 and 6, in Table 1.
  • 81
    • 0141473368 scopus 로고    scopus 로고
    • note
    • 2), and r(PO) can be estimated using original values of respective B parts, but estimated values of -0.20, -0.15, -0.55, and -0.65, respectively, infer that a phosphoryl group generates less steric strain than ethyl group. It means that a nitroxide carrying an ethyl group instead a phenyl or phosphored groups should be as good than these latter.
  • 82
    • 0007339787 scopus 로고
    • D, B., Ed.; Research Studies Press: J. Wiley & Sons: New York
    • Shorter, J. In Correlation Analysis of Organic Reactivity; D, B., Ed.; Research Studies Press: J. Wiley & Sons: New York, 1982; p 73.
    • (1982) Correlation Analysis of Organic Reactivity , pp. 73
    • Shorter, J.1
  • 84
    • 0141696658 scopus 로고    scopus 로고
    • note
    • It is not clear how the authors in refs 26 and 47 reached the value of r(Ph), so some cautions have to be taken. Furthermore, different values of r(Ph) can be also estimated from ref 35.
  • 88
    • 0141584153 scopus 로고    scopus 로고
    • note
    • Although 25 does not lie outside of the correlation in Figure 3, it will be considered as an outlier because it is capable of IHB as 26 and 27.
  • 89
    • 0141472556 scopus 로고    scopus 로고
    • note
    • Recently, X-Ray of 27 were obtained in Tordo's group and corroborate an IHB between hydroxyl and phosphoryl groups as depicted. (Equation Presented)


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